EP0158099A2 - Process for preparing aqueous dispersions and their use in the preparation of metallized coating compositions - Google Patents

Process for preparing aqueous dispersions and their use in the preparation of metallized coating compositions Download PDF

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Publication number
EP0158099A2
EP0158099A2 EP85102294A EP85102294A EP0158099A2 EP 0158099 A2 EP0158099 A2 EP 0158099A2 EP 85102294 A EP85102294 A EP 85102294A EP 85102294 A EP85102294 A EP 85102294A EP 0158099 A2 EP0158099 A2 EP 0158099A2
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EP
European Patent Office
Prior art keywords
weight
acid
resin
water
aqueous dispersions
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EP85102294A
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German (de)
French (fr)
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EP0158099B1 (en
EP0158099A3 (en
Inventor
Hans-Georg Dr. Stahl
Jürgen Dr. Schwindt
Klaus Dr. Nachtkamp
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Dr Johannes G Stahl Te Wardenburg Bondsrepublie
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Bayer AG
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type
    • B05D7/532—Base coat plus clear coat type the two layers being cured or baked together, i.e. wet on wet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/067—Metallic effect
    • B05D5/068—Metallic effect achieved by multilayers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/38—Paints containing free metal not provided for above in groups C09D5/00 - C09D5/36
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen

Definitions

  • the invention relates to a process for the production of aqueous dispersions based on a polyester, alkyd resin or polyacrylate resin dispersion, aluminum bronze, and to the use of these dispersions for the production of metallic effect coatings.
  • Metal effect paints are very popular, particularly among motor vehicle buyers.
  • For the coating one primarily uses the two-layer wet-on-wet painting process, whereby first a pigmented, aluminum bronze-containing basecoat is sprayed on, which is sprayed with a clear lacquer after a brief intermediate flashing without intermediate baking. Both layers are then baked together.
  • This two-layer painting process combines production reliability with the high technical quality of the paintwork obtained. In terms of environmental protection and raw material costs, it is desirable to use the paints in the form of aqueous dispersions.
  • the main problem with metallic-effect two-layer coating when using aqueous dispersions is reduced adhesion of the clearcoat to the basecoat and an uneven metallic effect.
  • European patent application 38 127 discloses aqueous basecoats for metallic-effect two-coat coatings based on a partially crosslinked polymeric microgel which has a pseudoplastic or thixotropic character.
  • European patent application 69 936 relates to a process for the preparation of aqueous dispersions which can be used as basecoats for metallic-effect two-coat coatings, where unsaturated compounds are polymerized in the presence of cellulose esters.
  • both registrations cannot solve the task described above.
  • a method leads to the goal, after which a binder dispersion pigment, aluminum bronze and an emulsifier.
  • a binder dispersion pigment, aluminum bronze and an emulsifier In this way, an immediately applicable aqueous metallic effect basecoat is obtained for the two-coat coating.
  • Basecoats produced from this exhibit excellent interlayer adhesion to the clearcoat and a metallic effect which remains intact when the clearcoat is applied wet-on-wet.
  • Another object of the invention is the use of dispersions prepared in this way for the production of metallic effect two-layer coatings.
  • alkyd resins are understood to mean polyesters modified with fatty acids, oils and isocyanates.
  • Acid components preferred for the synthesis of the polyesters or alkyd resins A are aliphatic, cycloaliphatic saturated or unsaturated and / or aromatic polybasic carboxylic acids, preferably di-, tri- and tetracarboxylic acids, with 2 to 14, preferably 4 to 12, carbon atoms per molecule or their derivatives capable of esterification (for example anhydrides or esters), for example phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydro- and hexahydrophthalic anhydride, endomethylene tetrahydrophthalic acid, Succinic acid, glutaric acid, sebacic acid, azelaic acid, trimellitic acid and trimellitic acid anhydride, pyromellitic acid anhydride, fumaric acid and maleic acid. Phthalic anhydride is the most common acid component.
  • the polyesters or alkyd resins A should not contain more than 20 mol%, based on the condensed
  • Alcohols preferred for the synthesis of the polyesters or alkyd resins A are aliphatic, cycloaliphatic and / or araliphatic alcohols with 1-15, preferably 2-6 C atoms, and 1-6, preferably 1-4, on non-aromatic C atoms bound OH groups per molecule, for example glycols such as ethylene glycol, 1,2-propanediol and -1,3, 1,2-butanediol, 1,3 and -1,4,2-1,3-propanediol -Ethylhexanediol-1,3, neopentylglycol, 2,2-trimethylpentanediol-1,3, hexanediol-1,6, cyclohexanediol-1,2 and -1,4, 1,2- and 1,4-bis- (hydroxymethyl) -cyclohexane, adipic acid bis (ethylene glycol ester); Ether alcohols such as di- and triethylene
  • Monocarboxylic acids preferred for the production of the polyesters or alkyd resins A are aliphatic, cycloaliphatic saturated and unsaturated and / or aromatic monocarboxylic acids with 3-24 carbon atoms per molecule, such as benzoic acid, p-tert-butylbenzoic acid, tolylic acid, hexahydrobenzoic acid, abietic acid and lactic acid.
  • the alkyd resins or polyester A can also contain monohydric alcohols such as methanol, propanol, cyclohexanol, 2-ethylhexanol, benzyl alcohol in amounts of up to 15% by weight, based on alkyd resin or polyester A, condensed. It is also possible to replace up to 25% of the ester bonds with urethane bonds.
  • monohydric alcohols such as methanol, propanol, cyclohexanol, 2-ethylhexanol, benzyl alcohol in amounts of up to 15% by weight, based on alkyd resin or polyester A, condensed. It is also possible to replace up to 25% of the ester bonds with urethane bonds.
  • the oil length calculated as triglyceride and based on the alkyd resin, is generally 5 to 50, preferably 20 to 40,% by weight.
  • the drying or non-drying fatty acids which generally contain 6 to 24 carbon atoms, can be used either as such or in the form of their glycerol esters (triglycerides).
  • Vegetable and animal oils, fats or fatty acids such as coconut oil, peanut oil, castor oil, wood oil, olive oil, soybean oil, linseed oil, cottonseed oil, safflower oil or oil fatty acid, and dehydrated castor oil or fatty acid are to be mentioned as preferred , monounsaturated fatty acids, lard, tallow and tears, Tall oil fatty acid and synthetic fatty acids, which can be produced by conjugation or isomerization from natural unsaturated oils or fatty acids.
  • Preferred saturated fatty acids are, for example, coconut oil fatty acids, ⁇ -ethylhexanoic acid, isononanoic acid (3,4,4-trimethylhexanoic acid) as well as palmitic and stearic acid and synthetic saturated branched fatty acids.
  • the number average molecular weight of the polyesters or alkyd resins A is 2000-10,000 (up to molecular weights of 5000 determined by vapor pressure osmometry in dioxane and acetone, the lower value being considered correct if the values differ; determined by membrane osmometry in molecular weights over 5000 in acetone).
  • Preferred polyacrylate resins A are obtained by copolymerization of vinyl or vinylidene monomers, such as styrene, oC-methylstyrene, o- or p-chlorostyrene, o-, m- or p-methylstyrene, p-tert-butylstyrene, (meth- ) Acrylic acid, (meth) acrylonitrile, acrylic and methacrylic acid alkyl esters with 1 to 8 carbon atoms in the alcohol component, for example ethyl acrylate, methyl acrylate, n- or iso-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isooctyl acrylate , tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, n- or iso-propy
  • Preferred monomers are styrene and (meth) acrylic acid alkyl esters with 1-8 C atoms in the alcohol component, the esterification product from fatty acid and hydroxyalkyl acrylates and mixtures thereof.
  • the polyacrylate resins A have average molecular weights M n from 1000-20,000, the molecular weights as described above for the polyesters or alkyd resins A can be determined.
  • the monomers are incorporated into the copolymer A in essentially the same proportions as are used for the polymerization, the copolymerized units being essentially randomly distributed.
  • Preferred isocyanates for the introduction of the urethane groups into the polyesters or alkyd resins I are poly Isocyanates with 4 to 25, preferably 4 to 16, carbon atoms and 2 to 4, preferably 2, isocyanate groups per molecule, that is to say aliphatic, cycloaliphatic, araliphatic and aromatic diisocyanates, as described, for example, in "Methods of Organic Chemistry” (Houben-Weyl ), Vol. 14/2, 4th edition, Georg Thieme Verlag, Stuttgart 1963, pp. 61-70, and by W. Siefken, Liebigs Ann. Chem.
  • aliphatic and cycloaliphatic polyisocyanates in particular hexamethylene diisocyanate, 4,4'-di (isocyanatocyclohexyl) methane and 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate.
  • Water-soluble aminoplast resins B in the sense of the invention are optionally modified and plasticized urea resins, melamine resins and guanamine and sulfonamide resins. These are condensation products of formaldehyde with urea, melamine, guanamine and sulfonamide; which are usually produced in an alkaline medium.
  • Preferred emulsifiers D are in Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 10, 449-473, Verlag Chemie, Weinheim 1975, and in Mc Cutcheon's "Detergents & Emulsifiers", McCutcheon Division, Mc Publishing Co., Glen Rock, N.J. (1979).
  • Preferred nonionic emulsifiers are compounds of the formula wherein R 1 and R 2 are an aliphatic, cycloaliphatic, araliphatic or aromatic group with 7-25 C atoms, round R 4 C 2 H 5 O, C 3 H 7 O or C 4 H 9 O and n integers of 3 mean to 100.
  • oligomers and polymers can also be used as emulsifiers or emulsion-stabilizing substances.
  • Surfactants which are particularly preferred for the preparation of the emulsifiers D are alkyl, acyl, aryl, alkylaryl polyglycol ethers which have 10-20 C atoms in the alkyl, acyl, aryl or alkylaryl radical and by alkoxylation of alkanols customary in surfactant chemistry, Carboxylic acids, phenols or alkylphenols with ethylene oxide and / or propylene oxide are formed. These ethylene oxide / propylene oxide mixed ethers can be block, mixed or mixed block adducts customary in surfactant chemistry.
  • Very preferred emulsifiers D are those derived from C 12 - 1S alkyl or C derived octyl- or Nonylphenylpolyethoxylaten that on average more than 10 ethylene oxide units, and preferably more than 20 ethylene oxide units per molecule, and mixtures thereof.
  • Preferred organic solvents E are those solvents which are miscible with water at room temperature.
  • auxiliaries F are, for example, water, leveling agents, thixotropic agents, wax-like substances such as ethylene copolymers, wetting agents, thickeners, preservatives and pigments.
  • the preparation can be carried out by producing a paste from components C and E, which is then coated with the alkyl resin dispersion.
  • a paste from components C and E, which is then coated with the alkyl resin dispersion.
  • one will prefer to produce a mixture consisting of components A-F.
  • the two-layer metallic effect coating can be baked at temperatures of 80 to 180 ° C, preferably 110 to 140 ° C.
  • Acid number of the alkyd resin 26 hydroxyl number of the alkyd resin: 144.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

Aqueous dispersions based on selected polyesters and/or acrylate resins, water-soluble aminoplast resins, emulsifiers, aluminium bronze, organic solvents and optionally further auxiliaries are suitable for the production of metal effect lacquer coatings by the two-layer wet-in-wet lacquering process.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung wäßriger Dispersionen auf Basis einer Polyester-, Alkydharz- oder Polyacrylatharzdispersion, Aluminiumbronze, sowie die Verwendung dieser Dispersionen zur Herstellung von Metalleffektlackierungen.The invention relates to a process for the production of aqueous dispersions based on a polyester, alkyd resin or polyacrylate resin dispersion, aluminum bronze, and to the use of these dispersions for the production of metallic effect coatings.

Metalleffektlackierungen erfreuen sich großer Beliebtheit, insbesondere bei den Käufern von Kraftfahrzeugen. Zur Beschichtung bedient man sich dabei vornehmlich des Zweischicht-Naß-in-Naß-Lackierverfahrens, wobei zunächst ein pigmentierter, Aluminiumbronze enthaltender Basislack aufgespritzt wird, der nach kurzer Zwischenablüftung ohne zwischenzeitliches Einbrennen mit einem Klarlack überspritzt wird. Beide Schichten werden anschließend gemeinsam eingebrannt. Dieses Zweischicht-Lackierverfahren vereinigt Produktionssicherheit mit hoher technischer Qualität der erhaltenen Lackierungen. Im Hinblick auf Umweltschutz und Rohstoffkosten ist es erwünscht, die Lacke in Form wäßriger Dispersionen einzusetzen.Metal effect paints are very popular, particularly among motor vehicle buyers. For the coating one primarily uses the two-layer wet-on-wet painting process, whereby first a pigmented, aluminum bronze-containing basecoat is sprayed on, which is sprayed with a clear lacquer after a brief intermediate flashing without intermediate baking. Both layers are then baked together. This two-layer painting process combines production reliability with the high technical quality of the paintwork obtained. In terms of environmental protection and raw material costs, it is desirable to use the paints in the form of aqueous dispersions.

Hauptproblem der Metalleffekt-Zweischicht-Lackierung bei Verwendung wäßriger Dispersionen ist eine verminderte Haftung des Klarlacks auf dem Basislack und ein ungleichmäßiger Metalleffekt.The main problem with metallic-effect two-layer coating when using aqueous dispersions is reduced adhesion of the clearcoat to the basecoat and an uneven metallic effect.

Zu beachten ist weiterhin, daß zur Lösung des erfindungsgemäßen Problems nur solche Maßnahmen tauglich erscheinen, die ohne allzu hohe Scherenergie auskommen, da andernfalls die blättchenförmigen Aluminiumbronzeteilchen zerstört werden und der erreichbare Metalleffekt leiden würde.It should also be noted that only those measures appear to be suitable for solving the problem according to the invention which can do without excessive shear energy, since otherwise the flaky aluminum bronze particles would be destroyed and the achievable metal effect would suffer.

Aus der europäischen Patentanmeldung 38 127 sind wäßrige Basislacke für Metalleffekt-Zweischicht-Lackierungen auf der Grundlage eines teilvernetzten polymeren Mikrogels bekannt, das pseudoplastischen oder thixotropen Charakter besitzt. Die europäische Patentanmeldung 69 936 betrifft ein Verfahren zur Herstellung wäßriger Dispersionen, die als Basislacke für Metalleffekt-Zweischicht-Lackierungen verwendet werden können, wobei ungesättigte Verbindungen in Gegenwart von Celluloseester polymerisiert werden. Beide Anmeldungen können jedoch die oben geschilderte Aufgabe nicht lösen.European patent application 38 127 discloses aqueous basecoats for metallic-effect two-coat coatings based on a partially crosslinked polymeric microgel which has a pseudoplastic or thixotropic character. European patent application 69 936 relates to a process for the preparation of aqueous dispersions which can be used as basecoats for metallic-effect two-coat coatings, where unsaturated compounds are polymerized in the presence of cellulose esters. However, both registrations cannot solve the task described above.

Überraschenderweise führt ein Verfahren zum Ziel, wonach man einer Bindemitteldispersion Pigment, Aluminiumbronze und einen Emulgator zugibt. Man erhält auf diese Weise einen unmittelbar applizierbaren wäßrigen Metalleffekt-Basislack für die Zweischicht-Lackierung. Daraus hergestellte Basislackierungen zeigen hervorragende Zwischenschichthaftung zum Klarlack und einen Metalleffekt, der beim Naß-in-Naß-Auftrag des Klarlacks störungsfrei erhalten bleibt.Surprisingly, a method leads to the goal, after which a binder dispersion pigment, aluminum bronze and an emulsifier. In this way, an immediately applicable aqueous metallic effect basecoat is obtained for the two-coat coating. Basecoats produced from this exhibit excellent interlayer adhesion to the clearcoat and a metallic effect which remains intact when the clearcoat is applied wet-on-wet.

Gegenstand der Erfindung ist also ein Verfahren zur Herstellung eines wäßrigen Metalleffekt-Basislacks auf Basis von

  • A) 10-30 Gew.-Teilen ölfreiem Polyester, Alkydharz und/oder Polyacrylatharz,
  • B) 2,5-15 Gew.-Teilen wasserlöslichem Aminoplastharz,
  • C) 2-10 Gew.-Teilen Aluminiumbronze,
  • D) 0,1-10 Gew.-Teilen nicht-ionischem Emulgator,
  • E) organischem Lösungsmittel und gegebenenfalls
  • F) weiteren Hilfsmitteln,

dadurch gekennzeichnet, daß man als Komponente A ein Harz mit einer Säurezahl von höchstens 30 und einer Hydroxylzahl von höchstens 150 verwendet und dieses in Form einer wäßrigen Dispersion mit einem Festkörpergehalt von 30 bis 50 Gew.-% mit den übrigen Komponenten mischt.The invention thus relates to a method for producing an aqueous metallic effect basecoat based on
  • A) 10-30 parts by weight of oil-free polyester, alkyd resin and / or polyacrylate resin,
  • B) 2.5-15 parts by weight of water-soluble aminoplast resin,
  • C) 2-10 parts by weight of aluminum bronze,
  • D) 0.1-10 parts by weight of nonionic emulsifier,
  • E) organic solvent and optionally
  • F) other aids,

characterized in that a resin with an acid number of at most 30 and a hydroxyl number of at most 150 is used as component A and this is mixed in the form of an aqueous dispersion with a solids content of 30 to 50% by weight with the other components.

Weiterer Gegenstand der Erfindung ist die Verwendung von derart hergestellten Dispersionen zur Herstellung von Metalleffekt-Zweischicht-Lackierungen.Another object of the invention is the use of dispersions prepared in this way for the production of metallic effect two-layer coatings.

Bevorzugte ölfreie Polyester und Alkydharze A) besitzen eine mittlere Funktionalität pro Molekül von 2,5 bis 10,

  • einen mittleren Kondensationsgrad pro Molekül von 10 bis 25, wobei der Kondensationsgrad die Summe der Monomerbausteine in der Kette des Polymermoleküls angibt,
  • einen mittleren Urethangruppengehalt pro Molekül von 3 bis 6 und
Preferred oil-free polyesters and alkyd resins A) have an average functionality per molecule of 2.5 to 10,
  • an average degree of condensation per molecule from 10 to 25, the degree of condensation indicating the sum of the monomer units in the chain of the polymer molecule,
  • an average urethane group content per molecule of 3 to 6 and

Reste einkondensierter 2.2-Di(hydroxymethyl)carbonsäuren und/oder Hydroxypivalinsäure entsprechend einer Säurezahl von 15 bis 30 enthalten, die zu mindestens 80 % neutralisiert sind.Contains of condensed 2,2-di (hydroxymethyl) carboxylic acids and / or hydroxypivalic acid corresponding to an acid number of 15 to 30, which are at least 80% neutralized.

Unter "Alkydharzen" werden in dieser Anmeldung fettsäure-, öl- und Isocyanat-modifizierte Polyester verstanden.In this application, “alkyd resins” are understood to mean polyesters modified with fatty acids, oils and isocyanates.

Für die Synthese der Polyester bzw. Alkydharze A bevorzugte Säurekomponenten sind aliphatische, cycloaliphatische gesättigte oder ungesättigte und/oder aromatische mehrbasische Carbonsäuren, vorzugsweise Di-, Tri- und Tetracarbonsäuren, mit 2 bis 14, vorzugsweise 4 bis 12 C-Atomen pro Molekül oder deren veresterungsfähige Derivate (z.B. Anhydride oder Ester), z.B. Phthalsäureanhydrid, Isophthalsäure, Terephthalsäure, Tetrahydro- und Hexahydrophthalsäureanhydrid, Endomethylentetrahydrophthalsäure, Bernsteinsäure, Glutarsäure, Sebacinsäure, Azelainsäure, Trimellithsäure und Trimellithsäureanhydrid, Pyromellithsäureanhydrid, Fumarsäure und Maleinsäure. Phthalsäureanhydrid ist die gebräuchlichste Säurekomponente. Die Polyester bzw. Alkydharze A sollen nicht mehr als 20 Mol-%, bezogen auf die einkondensierten Polycarbonsäurereste, Fumar- und Maleinsäurereste enthalten.Acid components preferred for the synthesis of the polyesters or alkyd resins A are aliphatic, cycloaliphatic saturated or unsaturated and / or aromatic polybasic carboxylic acids, preferably di-, tri- and tetracarboxylic acids, with 2 to 14, preferably 4 to 12, carbon atoms per molecule or their derivatives capable of esterification (for example anhydrides or esters), for example phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydro- and hexahydrophthalic anhydride, endomethylene tetrahydrophthalic acid, Succinic acid, glutaric acid, sebacic acid, azelaic acid, trimellitic acid and trimellitic acid anhydride, pyromellitic acid anhydride, fumaric acid and maleic acid. Phthalic anhydride is the most common acid component. The polyesters or alkyd resins A should not contain more than 20 mol%, based on the condensed-in polycarboxylic acid residues, fumaric and maleic acid residues.

Für die Synthese der Polyester bzw. Alkydharze A bevorzugte Alkohole sind aliphatische, cycloaliphatische und/oder araliphatische Alkohole mit 1-15, vorzugsweise 2-6 C-Atomen, und 1-6, vorzugsweise 1-4, an nicht-aromatische C-Atome gebundenen OH-Gruppen pro Molekül, z.B. Glykole wie'Ethylenglykol, Propandiol-1,2 und -1,3, Butandiol-1,2, -1,3, und -1,4, 2-Ethylpropandiol-1,3, 2-Ethylhexandiol-1,3, Neopentylglykol, 2,2-Trimethylpentandiol-1,3, Hexandiol-1,6, Cyclohexandiol-1,2 und -1,4, 1,2- und 1,4-Bis-(hydroxymethyl)-cyclohexan, Adipinsäure-bis-(ethylenglykolester); Etheralkohole wie Di- und Triethylenglykol, Dipropylenglykol; Dimethylolpropionsäure, oxalkylierte Bisphenole mit zwei C2-C3-Oxalkylgruppen pro Molekül, perhydrierte Bisphenole; Butantriol-1,2,4, Hexantriol-1,2,6, Trimethylolethan, Trimethylolpropan, Trimethylolhexan, Glycerin, Pentaerythrit, Dipentaerythrit, Mannit und Sorbit; kettenabbrechende einwertige Alkohole mit 1 bis 8 Kohlenstoffatomen wie Propanol, Butanol, Cyclohexanol und Benzylalkohol, Hydroxypivalinsäure. Die gebräuchlichsten Alkohole sind Glycerin, Trimethylolpropan, Neopentylglykol und Pentaerythrit.Alcohols preferred for the synthesis of the polyesters or alkyd resins A are aliphatic, cycloaliphatic and / or araliphatic alcohols with 1-15, preferably 2-6 C atoms, and 1-6, preferably 1-4, on non-aromatic C atoms bound OH groups per molecule, for example glycols such as ethylene glycol, 1,2-propanediol and -1,3, 1,2-butanediol, 1,3 and -1,4,2-1,3-propanediol -Ethylhexanediol-1,3, neopentylglycol, 2,2-trimethylpentanediol-1,3, hexanediol-1,6, cyclohexanediol-1,2 and -1,4, 1,2- and 1,4-bis- (hydroxymethyl) -cyclohexane, adipic acid bis (ethylene glycol ester); Ether alcohols such as di- and triethylene glycol, dipropylene glycol; Dimethylolpropionic acid, oxalkylated bisphenols with two C 2 -C 3 oxalkyl groups per molecule, perhydrogenated bisphenols; 1,2-butanetriol, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, trimethylolhexane, glycerol, pentaerythritol, dipentaerythritol, mannitol and sorbitol; chain-terminating monohydric alcohols with 1 to 8 carbon atoms such as propanol, butanol, cyclohexanol and benzyl alcohol, hydroxypivalic acid. The most common alcohols are glycerin, trimethylolpropane, neopentyl glycol and pentaerythritol.

Für die Herstellung der Polyester bzw. Alkydharze A bevorzugte Monocarbonsäuren sind aliphatische, cycloaliphatische gesättigte und ungesättigte und/oder aromatische Monocarbonsäuren mit 3-24 C-Atomen pro Molekül wie Benzoesäure, p-tert.-Butylbenzoesäure, Tolylsäure, Hexahydrobenzoesäure, Abietinsäure und Milchsäure.Monocarboxylic acids preferred for the production of the polyesters or alkyd resins A are aliphatic, cycloaliphatic saturated and unsaturated and / or aromatic monocarboxylic acids with 3-24 carbon atoms per molecule, such as benzoic acid, p-tert-butylbenzoic acid, tolylic acid, hexahydrobenzoic acid, abietic acid and lactic acid.

Die Alkydharze bzw. Polyester A können auch einwertige Alkohole wie Methanol, Propanol, Cyclohexanol, 2-Ethylhexanol, Benzylalkohol in Mengen bis zu 15 Gew.-%, bezogen auf Alkydharz bzw. Polyester A, einkondensiert enthalten. Ebenso ist es möglich, bis zu 25 % der Esterbindungen durch Urethanbindungen zu ersetzen.The alkyd resins or polyester A can also contain monohydric alcohols such as methanol, propanol, cyclohexanol, 2-ethylhexanol, benzyl alcohol in amounts of up to 15% by weight, based on alkyd resin or polyester A, condensed. It is also possible to replace up to 25% of the ester bonds with urethane bonds.

In den Alkydharzen A beträgt die Öllänge, berechnet als Triglycerid und bezogen auf das Alkydharz, in der Regel 5 bis 50, vorzugsweise 20 bis 40 Gew.-%. Die trocknenden oder nichttrocknenden Fettsäuren, die im allgemeinen 6 bis 24 C-Atome enthalten, können entweder als solche oder in Form ihrer Glycerinester (Triglyceride) eingesetzt werden.In the alkyd resins A, the oil length, calculated as triglyceride and based on the alkyd resin, is generally 5 to 50, preferably 20 to 40,% by weight. The drying or non-drying fatty acids, which generally contain 6 to 24 carbon atoms, can be used either as such or in the form of their glycerol esters (triglycerides).

Als bevorzugt sind pflanzliche und tierische öle, Fette oder Fettsäuren zu nennen, wie z.B. Kokos-, Erdnuß-, Ricinus-, Holz-, Oliven-, Sojabohnen-, Lein-, Baumwollsaatöl, Saffloröl oder -ölfettsäuren, dehydratisiertes Ricinusöl bzw. -fettsäure, einfach ungesättigte Fettsäuren, Schmalz, Talg und Trane, Tallölfettsäure sowie synthetische Fettsäuren, die durch Konjugierung oder Isomerisierung aus natürlichen ungesättigten ölen oder Fettsäuren hergestellt sein können. Bevorzugte gesättigte Fettsäuren sind z.B. Kokosölfettsäuren, ∝-Ethylhexansäure, Isononansäure (3,4,4-Trimethylhexansäure) sowie Palmitin- und Stearinsäure und synthetische gesättigte verzweigte Fettsäuren.Vegetable and animal oils, fats or fatty acids, such as coconut oil, peanut oil, castor oil, wood oil, olive oil, soybean oil, linseed oil, cottonseed oil, safflower oil or oil fatty acid, and dehydrated castor oil or fatty acid are to be mentioned as preferred , monounsaturated fatty acids, lard, tallow and tears, Tall oil fatty acid and synthetic fatty acids, which can be produced by conjugation or isomerization from natural unsaturated oils or fatty acids. Preferred saturated fatty acids are, for example, coconut oil fatty acids, ∝-ethylhexanoic acid, isononanoic acid (3,4,4-trimethylhexanoic acid) as well as palmitic and stearic acid and synthetic saturated branched fatty acids.

Das als Zahlenmittel bestimmte Molekulargewicht der Polyester bzw. Alkydharze A beträgt 2000 - 10.000 (bis zu Molekulargewichten von 5000 dampfdruckosmometrisch bestimmt in Dioxan und Aceton, wobei bei differierenden Werten der niedrigere Wert als korrekt angesehen wird; bei Molekulargewichten über 5000 membranosmometrisch in Aceton bestimmt).The number average molecular weight of the polyesters or alkyd resins A is 2000-10,000 (up to molecular weights of 5000 determined by vapor pressure osmometry in dioxane and acetone, the lower value being considered correct if the values differ; determined by membrane osmometry in molecular weights over 5000 in acetone).

Bevorzugte Polyacrylatharze A erhält man durch Copolymerisation von Vinyl- bzw. Vinylidenmonomeren, wie z.B. Styrol, oC-Methylstyrol, o- bzw. p-Chlorstyrol, o-, m-oder p-Methylstyrol, p-tert.-Butylstyrol, (Meth-) Acrylsäure, (Meth-)Acrylnitril, Acryl- und Methacrylsäurealkylester mit 1 bis 8 C-Atomen in der Alkoholkomponente, beispielsweise Ethylacrylat, Methylacrylat, n- bzw. iso-Propylacrylat, n-Butylacrylat, 2-Ethylhexylacrylat, 2-Ethylhexylmethacrylat, Isooctylacrylat, tert.-Butylacrylat, Methylmethacrylat, Ethylmethacrylat, n- bzw. iso-Propylmethacrylat, Butylmethacrylat, Isooctylmethacrylat und gegebenenfalls Mischungen derselben; Hydroxyalkyl(meth)acrylate mit 2-4 C-Atomen in der Alkylgruppe, z.B. 2-Hydroxyethyl-(meth)-acrylat, 2-Hydroxypropyl(meth-)acrylat, 4-Hy- droacybutyl(meth-)acrylat; Trimethylolpropanmono(meth-)-acrylat, Pentaerythritmono(meth)-acrylat und deren Ester mit Fettsäuren, Diester der Fumarsäure, Itaconsäure, Maleinsäure mit 4-8 Kohlenstoffatomen in der Alkoholkomponente; Acrylnitril, (Meth)acrylsäureamid, Vinylester von Alkanmonocarbonsäuren mit 2-5 Kohlenstoffatomen wie Vinylacetat oder Vinylpropionat oder Mischungen der genannten Monomeren, N-Methoxymethyl(meth)acrylsäureamid.Preferred polyacrylate resins A are obtained by copolymerization of vinyl or vinylidene monomers, such as styrene, oC-methylstyrene, o- or p-chlorostyrene, o-, m- or p-methylstyrene, p-tert-butylstyrene, (meth- ) Acrylic acid, (meth) acrylonitrile, acrylic and methacrylic acid alkyl esters with 1 to 8 carbon atoms in the alcohol component, for example ethyl acrylate, methyl acrylate, n- or iso-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isooctyl acrylate , tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, n- or iso-propyl methacrylate, butyl methacrylate, isooctyl methacrylate and optionally mixtures thereof; Hydroxyalkyl (meth) acrylates with 2-4 C atoms in the alkyl group, for example 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydrocybutyl (meth) acrylate; Trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate and their esters with fatty acids, diesters of fumaric acid, itaconic acid, maleic acid with 4-8 carbon atoms in the alcohol component; Acrylonitrile, (meth) acrylic acid amide, vinyl ester of alkane monocarboxylic acids with 2-5 carbon atoms such as vinyl acetate or vinyl propionate or mixtures of the monomers mentioned, N-methoxymethyl (meth) acrylic acid amide.

Bevorzugte Monomere sind Styrol und (Meth)Acrylsäurealkylester mit 1-8 C-Atomen in der Alkoholkomponente, dasVeresterungsprodukt aus Fettsäure und Hydroxyalkylacrylaten und deren Mischungen.Preferred monomers are styrene and (meth) acrylic acid alkyl esters with 1-8 C atoms in the alcohol component, the esterification product from fatty acid and hydroxyalkyl acrylates and mixtures thereof.

Die Polyacrylatharze A besitzen mittlere Molekulargewichte M n von 1000-20 000, wobei die Molekulargewichte wie oben für die Polyester bzw. Alkydharze A beschrieben, bestimmt werden können.The polyacrylate resins A have average molecular weights M n from 1000-20,000, the molecular weights as described above for the polyesters or alkyd resins A can be determined.

Die Monomeren werden im wesentlichen in den gleichen Verhältnissen, wie sie zur Polymerisation eingesetzt sind, in das Copolymerisat A eingebaut, wobei die einpolymerisierten Einheiten im wesentlichen statistisch verteilt sind.The monomers are incorporated into the copolymer A in essentially the same proportions as are used for the polymerization, the copolymerized units being essentially randomly distributed.

Bevorzugte Isocyanate für die Einführung der Urethangruppen in die Polyester bzw. Alkydharze I sind Polyisocyanate mit 4 bis 25, vorzugsweise 4 bis 16, C-Atomen und 2 bis 4, vorzugsweise 2, Isocyanatgruppen pro Molekül, also aliphatische, cycloaliphatische, araliphatische und aromatische Diisocyanate, wie sie beispielsweise in "Methoden der Organischen Chemie" (Houben-Weyl), Bd. 14/2, 4. Aufl., Georg Thieme Verlag, Stuttgart 1963, S. 61-70, und von W. Siefken, Liebigs Ann. Chem. 562, 75-136, beschrieben werden, z.B. 1,2-Ethylendiisoyanat, 1,4-Tetramethylendiisocyanat, 1,6-Hexamethylendiisocyanat, 2,2,4- bzw. 2,4,4-Trimethyl-1,6-hexamethylendiisocyanat, 1,12-Dodecandiisocyanat, ω,ω'-Diisocyanatodipropyl- ether, Cyclobutan-1,3-diisocyanat, Cyclohexan-1,3- und -1,4-diisocyanat, 2,2- und 2,6-Diisocyanato-1-methylcyclohexan, 3-Isocyanatomethyl-3,5,5-trimethylcyclohexyl- isocyanat ("Isophorondiisocyanat"), 2,5- und 3,5-Bis-(isocyanatomethyl)-8-methyl-1,4-methano-decahydronaptha- lin, 1,5-, 2,5-, 1,6- und 2,6-Bis(isocyanatomethyl)-4,7- methano-hexahydroindan, 1,5-, 2,5-, 1,6- und,2,6-Bis-(isocyanato)-4,7-methano-hexahydroindan, Dicyclohexyl-2,4'- und -4,4'-diisocyanat, 2,4- und 2,6-Hexahydrotoluylendiisocyanat, Perhydro-2,4'- und -4,4'-diphenylmethandiisocyanat, ω,ω'-Diisocyanato-1,4-diethylbenzol, 1,3- und 1,4-Phenylendiisocyanat, 4,4'-Diisocyanato-diphenyl, 4,4'-Diisocyanato-3,3'-dichlordiphenyl, 4,4'-Diisocyanato-3,3'-dimethoxy-diphenyl, 4,4'-Diisocyanato-3,3'-dimethyl-diphenyl, 4,4'-Diisocyanato-3,31-diphenyl- diphenyl, 2,41- und 4,4'-Diisocyanato-diphenylmethan, Naphthylen-1,5-diisocyanat, Toluylendiisocyanate wie 2,4- bzw. 2,6-Toluylen-diisocyanat, N,N'-(4,4'-Dimethyl-3,31-Diisocyanatodiphenyl)-uretdion, m-Xylylen-diisocyanat, aber auch die Triisocyanate wie 2,4,4'-Triisocyanato-diphenylether, 4,4',4"-Triisocyanatotriphenylmethan, Tris(4-isocyanatophenyl)-thiophosphat, sowie beliebige Gemische dieser Isomeren.Preferred isocyanates for the introduction of the urethane groups into the polyesters or alkyd resins I are poly Isocyanates with 4 to 25, preferably 4 to 16, carbon atoms and 2 to 4, preferably 2, isocyanate groups per molecule, that is to say aliphatic, cycloaliphatic, araliphatic and aromatic diisocyanates, as described, for example, in "Methods of Organic Chemistry" (Houben-Weyl ), Vol. 14/2, 4th edition, Georg Thieme Verlag, Stuttgart 1963, pp. 61-70, and by W. Siefken, Liebigs Ann. Chem. 562, 75-136, can be described, for example 1,2-ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4- or 2,4,4-trimethyl-1,6- hexamethylene diisocyanate, 1,12-dodecane diisocyanate, ω, ω'-diisocyanatodipropyl ether, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, 2,2- and 2,6-diisocyanato- 1-methylcyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate ("isophorone diisocyanate"), 2,5- and 3,5-bis- (isocyanatomethyl) -8-methyl-1,4-methano-decahydronaptha- lin, 1,5 - , 2,5-, 1,6- and 2,6-bis (isocyanatomethyl) -4,7-methano-hexahydroindane, 1,5-, 2,5-, 1,6- and, 2,6-bis (isocyanato) -4,7-methano-hexahydroindane, dicyclohexyl-2,4'- and -4,4'-diisocyanate, 2,4- and 2,6-hexahydrotoluenediisocyanate, perhydro-2,4 '- and -4,4'-diphenylmethane diisocyanate, ω, ω'-diisocyanato-1,4-diethylbenzene, 1,3- and 1,4-phenylene diisocyanate, 4,4'-diisocyanato-diphenyl, 4,4'-diisocyanato -3,3'-dichlorodiphenyl, 4,4'-diisocyanato-3,3'-dimethoxydiphenyl, 4,4'-diisocyanato-3, 3'-dimethyl-diphenyl, 4,4'-diisocyanato-diphenyl- 1- 3.3 diphenyl, 2.4 1- and 4,4'-diisocyanato-diphenylmethane, naphthylene-1,5-diisocyanate, toluene diisocyanates such as 2, 4- or 2,6-tolylene diisocyanate, N 'N - (4,4-dimethyl-3,3 1- diisocyanatodiphenylmethane) uretdione, m-xylylene diisocyanate, but also the triisocyanates such as 2,4, 4'-triisocyanatodiphenyl ether, 4,4 ', 4 "triisocyanatotriphenyl methane, tris (4-isocyanatophenyl) thiophosphate, as well as any mixtures of these isomers.

Besonders bevorzugt werden in der Regel die technisch leicht zugänglichen aliphatischen und cycloaliphatischen Polyisocyanate, insbesondere Hexamethylendiisocyanat, 4,4'-Di(isocyanatocyclohexyl)-methan und 3-Isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanat.As a rule, particularly preferred are the technically easily accessible aliphatic and cycloaliphatic polyisocyanates, in particular hexamethylene diisocyanate, 4,4'-di (isocyanatocyclohexyl) methane and 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate.

Wasserlösliche Aminoplastharze B im Sinne der Erfindung sind gegebenenfalls modifizierte und plastifizierte Harnstoffharze, Melaminharze sowie Guanamin-und Sulfonamidharze. Es handelt sich dabei jeweils um Kondensationsprodukte von Formaldehyd mit Harnstoff, Melamin, Guanamin und Sulfonamid; die üblicherweise im alkalischen Medium hergestellt werden.Water-soluble aminoplast resins B in the sense of the invention are optionally modified and plasticized urea resins, melamine resins and guanamine and sulfonamide resins. These are condensation products of formaldehyde with urea, melamine, guanamine and sulfonamide; which are usually produced in an alkaline medium.

Bevorzugte Emulgatoren D sind in Ullmann's Encyclopädie der technischen Chemie, 4. Auflage, Band 10, 449-473, Verlag Chemie, Weinheim 1975, und in Mc Cutcheon's "Detergents & Emulsifiers", McCutcheon Division, Mc Publishing Co., Glen Rock, N.J. (1979) beschrieben.Preferred emulsifiers D are in Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 10, 449-473, Verlag Chemie, Weinheim 1975, and in Mc Cutcheon's "Detergents & Emulsifiers", McCutcheon Division, Mc Publishing Co., Glen Rock, N.J. (1979).

Bevorzugte nichtionische Emulgatoren sind Verbindungen der Formel

Figure imgb0001
worin R 1 und R2 eine aliphatische, cycloaliphatische, araliphatische oder aromatische Gruppe mit 7-25 C-Atomen, Rund R4 C2H5O, C3H7O oder C4H9O und mund n ganze Zahlen von 3 bis 100 bedeuten.Preferred nonionic emulsifiers are compounds of the formula
Figure imgb0001
 wherein R 1 and R 2 are an aliphatic, cycloaliphatic, araliphatic or aromatic group with 7-25 C atoms, round R 4 C 2 H 5 O, C 3 H 7 O or C 4 H 9 O and n integers of 3 mean to 100.

Ferner sind auch Oligomere und Polymere als Emulgatoren oder emulsionsstabilisierende Substanzen verwendbar. Darunter fallen z.B. Schutzkolloide wie Casein, teilweise und völlig verseiftes Polyvinylacetat, Polymerisate und Copolymerisate aus Vinylpyrrolidon.Furthermore, oligomers and polymers can also be used as emulsifiers or emulsion-stabilizing substances. This includes e.g. Protective colloids such as casein, partially and completely saponified polyvinyl acetate, polymers and copolymers of vinyl pyrrolidone.

Für die Herstellung der Emulgatoren D besonders bevorzugte Tenside sind Alkyl-, Acyl-, Aryl-, Alkylarylpolyglykolether, die 10-20 C-Atome im Alkyl-, Acyl-, Aryl-oder Alkylarylrest aufweisen und durch Alkoxylierung von in der Tensidchemie üblichen Alkanolen, Carbonsäuren, Phenolen oder Alkylphenolen mit Ethylenoxid und/oder Propylenoxid entstehen. Bei diesen Ethylenoxid/Propylenoxid-mischethern kann es sich um in der Tensidchemie übliche Block-, Misch- oder Mischblockaddukte handeln.Surfactants which are particularly preferred for the preparation of the emulsifiers D are alkyl, acyl, aryl, alkylaryl polyglycol ethers which have 10-20 C atoms in the alkyl, acyl, aryl or alkylaryl radical and by alkoxylation of alkanols customary in surfactant chemistry, Carboxylic acids, phenols or alkylphenols with ethylene oxide and / or propylene oxide are formed. These ethylene oxide / propylene oxide mixed ethers can be block, mixed or mixed block adducts customary in surfactant chemistry.

Ganz bevorzugte Emulgatoren D sind solche, die sich von C 12-C 1S-Alkyl- oder Octyl- oder Nonylphenylpolyethoxylaten ableiten, die im Mittel mehr als 10 Ethylenoxideinheiten und vorzugsweise mehr als 20 Ethylenoxideinheiten pro Molekül aufweisen, sowie deren Mischungen.Very preferred emulsifiers D are those derived from C 12 - 1S alkyl or C derived octyl- or Nonylphenylpolyethoxylaten that on average more than 10 ethylene oxide units, and preferably more than 20 ethylene oxide units per molecule, and mixtures thereof.

Bevorzugte organische Lösungsmittel E sind solche Lösungsmittel, die bei Raumtemperatur mit Wasser mischbar sind.Preferred organic solvents E are those solvents which are miscible with water at room temperature.

Weitere Hilfsmittel F sind beispielsweise Wasser, Verlaufshilfsmittel, Thixotropiermittel, wachsähnliche Stoffe, wie Ethylen-Copolymerisate, Netzmittel, Verdicker, Konservierungsmittel und Pigmente.Other auxiliaries F are, for example, water, leveling agents, thixotropic agents, wax-like substances such as ethylene copolymers, wetting agents, thickeners, preservatives and pigments.

Die Herstellung kann im Prinzip so erfolgen, daß man aus den Komponenten C und E eine Paste herstellt, die man dann mit der Alkylharzdispersion auflackt. In der Regel wird man jedoch vorziehen, eine Mischung bestehend aus den Komponenten A-F herzustellen.In principle, the preparation can be carried out by producing a paste from components C and E, which is then coated with the alkyl resin dispersion. As a rule, however, one will prefer to produce a mixture consisting of components A-F.

Beide Herstellungsmethoden gewährleisten, daß die Aluminiumbronze homogen in den einzelnen Teilchen der dispersen Phase verteilt ist.Both production methods ensure that the aluminum bronze is homogeneously distributed in the individual particles of the disperse phase.

Die Zweischicht-Metalleffekt-Lackierung kann bei Temperaturen von 80 bis 180°C, vorzugsweise 110 bis 140°C eingebrannt werden.The two-layer metallic effect coating can be baked at temperatures of 80 to 180 ° C, preferably 110 to 140 ° C.

Beispiel 1example 1 a) Zusammensetzung der Alkydharzdispersion:a) Composition of the alkyd resin dispersion:

  • 11,88 Gew.-% hydrierte C16-C18-Fettsäuren,11.88% by weight of hydrogenated C 16 -C 18 fatty acids,
  • 7,82 Gew.-% Trimethylolpropan,7.82% by weight trimethylolpropane,
  • 3,32 Gew.-% Pentaerythrit,3.32% by weight of pentaerythritol,
  • 7,57 Gew.-% Phthalsäureanhydrid,7.57% by weight of phthalic anhydride,
  • 2,48 Gew.-% Dimethylolpropionsäure,2.48% by weight of dimethylolpropionic acid,
  • 8,31 Gew.-% "Isophoron"diisocyanat,8.31% by weight of "isophorone" diisocyanate,
  • 1,49 Gew.-% Triethylamin,1.49% by weight of triethylamine,
  • 5,94 Gew.-% N-Methylpyrrolidon,5.94% by weight of N-methylpyrrolidone,
  • 0,4 Gew.-% Polyethylenoxid (auf Nonylphenol gestartet, durchschnittliche 20 Ethylenoxideinheiten pro Molekül),0.4% by weight of polyethylene oxide (started on nonylphenol, average 20 ethylene oxide units per molecule),
  • 50,79 Gew.-% Wasser.50.79 wt% water.

Säurezahl des Alkydharzes : 26, Hydroxyzahl des Alkydharzes : 144.Acid number of the alkyd resin: 26, hydroxyl number of the alkyd resin: 144.

b) Lackherstellung:b) Paint production:

(1) Aufschlämmung von 50 g Aluminiumpaste, 65 gew.- %-ig in Wasser (

Figure imgb0002
32,5 g Aluminium), in 50 g Butylacetat;
Auflackung mit

  • 144 g Alkydharzdispersion (a) (
    Figure imgb0003
    67,7 g Alkydharz),
  • 35 g wasserlöslichem Melaminharz, 80 gew.-%-ig in Wasser (
    Figure imgb0004
    28 g Melaminharz),
  • 20 g (3-Benzyl-4-hydroxy-biphenyl)-polyglykolether,
  • 15 g wasserverdünnbarem Polyurethan (Borchigel L 75) und
  • 130 g Wasser zur Viskositätseinstellung.
(1) Slurry of 50 g of aluminum paste, 65% by weight in water (
Figure imgb0002
32.5 g aluminum), in 50 g butyl acetate;
Paint with
  • 144 g alkyd resin dispersion (a) (
    Figure imgb0003
    67.7 g alkyd resin),
  • 35 g water-soluble melamine resin, 80% by weight in water (
    Figure imgb0004
    28 g melamine resin),
  • 20 g (3-benzyl-4-hydroxy-biphenyl) polyglycol ether,
  • 15 g water-borne polyurethane (Borchigel L 75) and
  • 130 g water for viscosity adjustment.

c) Verarbeitung:

  • Der Lack (b) wurde mittels Spritzpistole auf ein grundiertes und gefülltes Karosserieteil aufgebracht. Nach 5 Minuten Ablüften wurde mit einem handelsüblichen, lösungsmittelhaltigen Acrylatharz überspritzt und bei 130°C 30 Minuten eingebrannt.
c) Processing:
  • The paint (b) was applied to a primed and filled body part using a spray gun. After flashing off for 5 minutes, a commercially available, solvent-containing acrylate resin was sprayed over and baked at 130 ° C. for 30 minutes.

d) Resultat:

  • Der Überzug zeigte einen hervorragenden Bronzestand (sowohl in Silbergrau als auch in Buntmetallic).
d) Result:
  • The coating showed an excellent bronze stand (both in silver gray and in non-ferrous metallic).

Beispiel 2Example 2

b) Anreibung in Bindemittel mit

  • 4 g Aluminiumpaste, 65 gew.-%-ig in Testbenzin/ Aromatengemisch (
    Figure imgb0005
    2,6 g Aluminium),
  • 5 g Aluminiumpaste, 65 gew.-%-ig in Wasser (
    Figure imgb0006
    3,25 g Aluminium),
  • 5 g Isopropanol,
  • 5 g Butylacetat,
  • 1 g (3-Benzyl-4-hydroxy-biphenyl)-polyglykolether,
  • 1 g auf Sorbit gestartetem Polypropylenoxid (Funktionalität 4.3, OH-Gehalt 14.5 Gew.-%, Molekulargewicht ca. 500),
  • 6 g Alkydharzdispersion 1 a, 47 gew.-%-ig in Wasser (
    Figure imgb0007
    2,82 g Alkydharz);
b) Grinding in binder with
  • 4 g aluminum paste, 65% by weight in white spirit / aromatic mixture (
    Figure imgb0005
    2.6 g aluminum),
  • 5 g aluminum paste, 65% by weight in water (
    Figure imgb0006
    3.25 g aluminum),
  • 5 g isopropanol,
  • 5 g butyl acetate,
  • 1 g (3-benzyl-4-hydroxy-biphenyl) polyglycol ether,
  • 1 g of polypropylene oxide started on sorbitol (functionality 4.3, OH content 14.5% by weight, molecular weight approx. 500),
  • 6 g alkyd resin dispersion 1 a, 47% by weight in water (
    Figure imgb0007
    2.82 g alkyd resin);

Auflackung mit

  • 26 g Alkydharzdispersion 1 a, 47 gew.-%-ig in Wasser (
    Figure imgb0008
    12,22 g Alkydharz),
  • 3 g wasserverdünnbarem Polyurethan (Borchigel L 75),
  • 1 g (3-Benzyl-4-hydroxy-biphenyl)-polyglykolether,
  • 1 g auf Sorbit gestartetem Polypropylenoxid (s.o.),
  • 5 g wasserlöslichem Melaminharz, 80 gew.-%-ig in Wasser (
    Figure imgb0009
    4 g Melaminharz), und
  • 30 g Wasser zur Viskositätseinstellung.
Paint with
  • 26 g alkyd resin dispersion 1 a, 47% by weight in water (
    Figure imgb0008
    12.22 g alkyd resin),
  • 3 g water-dilutable polyurethane (Borchigel L 75),
  • 1 g (3-benzyl-4-hydroxy-biphenyl) polyglycol ether,
  • 1 g of polypropylene oxide started on sorbitol (see above),
  • 5 g water-soluble melamine resin, 80% by weight in water (
    Figure imgb0009
    4 g melamine resin), and
  • 30 g water for viscosity adjustment.

(c) und (d) wie in Beispiel 1.(c) and (d) as in Example 1.

Claims (2)

1. Verfahren zur Herstellung eines wäßrigen Metalleffekt-Basislacks auf Basis von A) 10-30 Gew.-Teilen ölfreiem Polyester, Alkydharz und/oder Polyacrylatharz, B) 2,5-15 Gew.-Teilen wasserlösliches Aminoplastharz, C) 2-10 Gew.-Teilen Aluminiumbronze, D) 0,1 - 10 Gew.-Teilen nicht- ionischem Emulgator, E) organischem Lösungsmittel und gegebenenfalls F) weiteren Hilfsmitteln,
dadurch gekennzeichnet, daß man als Komponente A ein Harz mit einer Säurezahl von höchstens 30 und einer Hydroxylzahl von höchstens 150 verwendet und dieses in Form einer wäßrigen Dispersion mit einem Festkörpergehalt von 30 bis 50 Gew.-% mit den übrigen Komponenten mischt.1. Process for the preparation of an aqueous metallic effect basecoat based on A) 10-30 parts by weight of oil-free polyester, alkyd resin and / or polyacrylate resin, B) 2.5-15 parts by weight of water-soluble aminoplast resin, C) 2-10 parts by weight of aluminum bronze, D) 0.1-10 parts by weight of nonionic emulsifier, E) organic solvent and optionally F) other aids,
characterized in that a resin with an acid number of at most 30 and a hydroxyl number of at most 150 is used as component A and this is mixed in the form of an aqueous dispersion with a solids content of 30 to 50% by weight with the other components. 2) Verwendung nach Verfahren gemäß Anspruch 1 hergestellter Dispersionen zur Herstellung von Metalleffekt-Zweischicht-Lackierungen.2) Use according to the method according to claim 1 dispersions for the production of metallic effect two-layer coatings.
EP85102294A 1984-03-13 1985-03-01 Process for preparing aqueous dispersions and their use in the preparation of metallized coating compositions Expired EP0158099B1 (en)

Priority Applications (1)

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AT85102294T ATE44755T1 (en) 1984-03-13 1985-03-01 PROCESSES FOR THE PRODUCTION OF AQUEOUS DISPERSIONS AND THEIR USE FOR THE PRODUCTION OF METAL EFFECT COATINGS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3409080 1984-03-13
DE19843409080 DE3409080A1 (en) 1984-03-13 1984-03-13 METHOD FOR PRODUCING AQUEOUS DISPERSIONS AND THE USE THEREOF FOR PRODUCING METAL EFFECT PAINTINGS

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EP0158099A2 true EP0158099A2 (en) 1985-10-16
EP0158099A3 EP0158099A3 (en) 1987-04-22
EP0158099B1 EP0158099B1 (en) 1989-07-19

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EP (1) EP0158099B1 (en)
JP (1) JPS60208372A (en)
AT (1) ATE44755T1 (en)
CA (1) CA1285087C (en)
DE (2) DE3409080A1 (en)
ES (1) ES8607372A1 (en)

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DE3739332A1 (en) * 1987-11-20 1989-06-01 Basf Lacke & Farben Process for the production of a multilayer, protective and/or decorative coating, and water-thinnable coating compositions
US6448326B1 (en) 1991-03-03 2002-09-10 Basf Coatings Ag Mixer system for the preparation of water-thinnable coating compositions
US6555612B1 (en) 1999-01-28 2003-04-29 Basf Coatings Ag Aqueous coating material and modular system for producing same
US6555613B1 (en) 1999-03-10 2003-04-29 Basf Coatings Ag Polyurethane and its use for producing solvent-free coating substances
DE102008009481A1 (en) 2008-02-15 2009-08-20 Basf Coatings Ag Aqueous coating composition, process for its preparation and its use
US8128744B2 (en) 2008-02-15 2012-03-06 BASF Coating GmbH Aqueous coating composition, method for production of the same, and use thereof
WO2014005932A1 (en) 2012-07-06 2014-01-09 Basf Se The use of carboxylic acid esters as lubricants

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DE3628123C1 (en) * 1986-08-19 1988-02-11 Herberts Gmbh Pigment dispersion and its use
DE3628125A1 (en) * 1986-08-19 1988-03-03 Herberts Gmbh AQUEOUS COATING AGENT, METHOD FOR THE PRODUCTION THEREOF AND THE USE THEREOF
DE3834738A1 (en) * 1988-10-12 1990-04-19 Basf Lacke & Farben METHOD FOR PRODUCING A MULTI-LAYER COATING, AQUEOUS COATING COMPOSITION, WATER-DISCOVERABLE POLYACRYLATE RESINS AND METHOD FOR PRODUCING WATER-DISCOVERABLE POLYACRYLATE RESINS
DE4315593C2 (en) * 1993-05-11 2001-06-13 Westdeutsche Farbengesellschaf Process for producing a two-component lacquer
DE10043405C1 (en) 2000-09-04 2002-06-27 Basf Coatings Ag Process for the production of color and / or effect coatings
EP1245603B1 (en) * 2001-03-30 2006-01-18 Kansai Paint Co., Ltd. Processes for producing aqueous alkyd resin dispersions
DE102014007805A1 (en) 2014-05-27 2015-12-03 WindplusSonne GmbH Solar absorber, process for its preparation and its use
DE102014013600A1 (en) 2014-09-13 2016-03-17 WindplusSonne GmbH Solar absorber, process for its preparation and its use
DE102018207815A1 (en) 2018-05-18 2019-11-21 Karl Wörwag Lack- Und Farbenfabrik Gmbh & Co. Kg Multilayer, color and / or effect paint system and method for forming a basecoat film

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Publication number Priority date Publication date Assignee Title
DE3739332A1 (en) * 1987-11-20 1989-06-01 Basf Lacke & Farben Process for the production of a multilayer, protective and/or decorative coating, and water-thinnable coating compositions
US6448326B1 (en) 1991-03-03 2002-09-10 Basf Coatings Ag Mixer system for the preparation of water-thinnable coating compositions
US6555612B1 (en) 1999-01-28 2003-04-29 Basf Coatings Ag Aqueous coating material and modular system for producing same
US6555613B1 (en) 1999-03-10 2003-04-29 Basf Coatings Ag Polyurethane and its use for producing solvent-free coating substances
DE102008009481A1 (en) 2008-02-15 2009-08-20 Basf Coatings Ag Aqueous coating composition, process for its preparation and its use
US8128744B2 (en) 2008-02-15 2012-03-06 BASF Coating GmbH Aqueous coating composition, method for production of the same, and use thereof
WO2014005932A1 (en) 2012-07-06 2014-01-09 Basf Se The use of carboxylic acid esters as lubricants
US9708564B2 (en) 2012-07-06 2017-07-18 Basf Se Use of carboxylic acid esters as lubricants

Also Published As

Publication number Publication date
JPS60208372A (en) 1985-10-19
ES541184A0 (en) 1986-05-16
DE3571635D1 (en) 1989-08-24
US4594374A (en) 1986-06-10
EP0158099B1 (en) 1989-07-19
EP0158099A3 (en) 1987-04-22
ATE44755T1 (en) 1989-08-15
DE3409080A1 (en) 1985-09-19
ES8607372A1 (en) 1986-05-16
CA1285087C (en) 1991-06-18

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